Russian Chemical Bulletin, International Edition, Vol. 63, No. 7, pp.

1539—1542, July, 2014 1539

Mass spectrometric studies of selfcondensation products of cyclohexanone

under alkaline conditions and synthesis of dodecahydrotriphenylene
and triphenylene from easily available reactants
I. S. Kovalev,a D. S. Kopchuk,a,b G. V. Zyryanov,a,b A. F. Khasanov,a V. L. Rusinov,a and O. N. Chupakhina,b

aUral Federal University named after the First President of Russia B. N. Yeltsin,
19 ul. Mira, 620002 Ekaterinburg, Russian Federation.
Email: [email protected]
I. Ya. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences,
20 ul. S. Kovalevskoy, 620219 Ekaterinburg, Russian Federation.
Email: [email protected]

LCMS was used to study products of cyclohexanone selfcondensation under alkaline

conditions. Improved methods (as compared to those described in the literature) for the prepa
ration of dodecahydrotriphenylene and highly pure sublimed triphenylene were suggested based
on the easily available and cheap reactants. Possible reasons of the low yield of the target
dodecahydrotriphenylene in the step of oligomerization of cyclohexanone were identified.

Key words: triphenylene, cyclohexanone, trimerization, aromatization.

At the present time, triphenylene (1) and its deriva well known methods which use readily available reagents,
tives are of considerable interest because of a possibility of in particular, cyclohexanone.24,25
their application as a base for the preparation of electrolu An approach to the preparation of dodecahydrotriphe
minescent materials,1 discotic liquid nylene 2 by the reaction of cyclohexanone with an alkali
crystals,2,3 and as chemosensors and described by German authors26 seems the most promis
sensor materials. 4,5 Unsubstituted ing, since it compares favorably with other methods by the
triphenylene can be easily functional absence of expensive reactants and catalysts (Scheme 1).
ized: in the literature, there are de The triol 3 results from the reaction of cyclohexanone
scribed methods for the preparation with the alkali at room temperature and its subsequent
of its monobromo,6,7 hexabromo,8,9 dehydration with orthophosphoric acid gives dodeca
monoiodo derivatives,10 various acyl hydrotriphenylene 2. We have chosen this procedure as
derivatives,11,12 as well as triphenylene2carbaldehyde.13 a basic one in the present work.
Thus, triphenylene 1 is a key compound in the preparation
of a wide variety of its derivatives necessary for different Scheme 1
purposes. The present work is devoted to the development
of an approach to the synthesis of triphenylene 1 from
easily available reagents.
A number of methods for the preparation of tri
phenylene 1 are described in the literature. In particular,
a preparative synthesis of triphenylene can be accom
plished using aryne intermediates,14—17 crosscoupling re
actions,18 metalcatalyzed arylation,19,20 cyclization based
on 9,10phenanthrenequinone.21 These methods have
a disadvantage of very expensive starting reagents and cat
alysts, as well as a necessity to purify triphenylene in order
to obtain highly pure product.
At the same time, one of the most promising methods
for the preparation of triphenylene is dehydrogenation22,23
of dodecahydro derivative in the presence of palladium
oncharcoal, which in turn can be obtained according to

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1539—1542, July, 2014.
10665285/14/63071539 © 2014 Springer Science+Business Media, Inc.
1540 Russ.Chem.Bull., Int.Ed., Vol. 63, No. 7, July, 2014 Kovalev et al.

The authors of the work26 found that the cyclic trimer 3 Table 1. The LCMS data for the reaction mixture obtained
was the only product of the reaction of cyclohexanone upon oligomerization of cyclohexane under alkaline conditionsa
with an alkali, whose existence was confirmed by IR spectro
scopy and elemental analysis. Com Chromatographic MS, Molecular
However, attempted reproduction of this method pound separation m/z, [M + H]+ formula
showed that oligomerization of cyclohexanone is accom ret Iintc Found Calculated
panied by the formation of considerably more complicat /min (rel. units)
ed mixture of products. It should be also noted that the
Dimers
yields of dodecahydrotriphenylene 2 obtained by this pro
cedure varied from low to moderate. To find possible rea 4а 19.7 114239 179.1436 179.1436 C12H18O
sons for this, we studied the composition of the reaction 4b 17.2 326589 179.1436 179.1436 C12H18O
mixtures formed upon oligomerization of cyclohexanone 5 17.2 6445 197.1532 197.1536 C12H20O 2
by LCMS. Trimers
According to the LCMS data, the reaction mixture 3 15.8 17703 295.2236 295.2268 C18H30O 3
obtained by treatment of cyclohexane with NaOH for three 16.0 17609 295.2237 295.2268 C18H30O 3
days contains the following intermediate compounds: de 17.3 25190 295.2233 295.2268 C18H30O 3
hydrated dimers of cyclohexanone 4 (two isomers), dimer 6 22.5 8700 277.2113 277.2162 C18H28O 2
of cyclohexanone 5, and isomers of cyclohexanone trimers 7 20.5 11660 259.2042 259.2056 C18H26O
with different degree of dehydration 3, 6, and 7 (Table 1, 22.5 47939 259.2042 259.2056 C18H26O
24.5 15084 259.2039 259.2056 C18H26O
Fig. 1, 2).
28.9 13772 259.2031 259.2056 C18H26O
aReaction conditions: cyclohexanone : NaOH = 3.8 : 1, 20 C,

3 days.
bCalculated based on the mass spectrometric data.
cIntegral intensity.

mixtures at room temperature; heating gave lower yields

of the target triphenylene 1. We also found that cyclohex
anone dimers 4a,b and 5 are present in the reaction mix
ture in large amounts, whereas the starting cyclohexanone
is completely absent. To sum up, there are no precondi
tion for the formation of the trimer and, therefore, of
dodecahydrotriphenylene 2, whereas tetramer is present

a
The peaks [M + H]+ of compounds with m/z 179.1436
(compounds 4a,b) and m/z 259.2042 (compound 7) have
the highest integral intensities.
The starting cyclohexanone was absent in the reaction
mixture: the distillation of the reaction mixtures gave no
fraction with b.p. 155 C, and no [M + H]+ peak of cyclo
hexanone with m/z 99.08 was observed according to the
15 20 ret/min
LCMS data.
Analysis of trimeric products of condensation of cyclo
b
hexanone 3 (three isomers), 6 and 7 (four isomers)
showed that, despite the presence of such products
(see Table 1) in the reaction mixture, the integral inten
sities of the peaks of these compounds are low, therefore,
a suggestion that the low yield of the reaction is ex
plained by the parallel processes of trimerization, lead
ing to the products incapable of further cyclization to
dodecahydrotriphenylene 2, was not confirmed. It can
be supposed that the oligomerization reaction of cyclo 15 20 ret/min
hexanone is kinetically controlled, since the best results Fig. 1. Chromatography pattern of cyclohexane dimers 4a,b (a)
were obtained after a prolonged standing of the reaction and 5 (b).
MS study of cyclohexane alkaline condensation Russ.Chem.Bull., Int.Ed., Vol. 63, No. 7, July, 2014 1541

a is considerably higher than that in the methods de

scribed earlier.
In conclusion, in the present work we developed an
approach to the synthesis of highly pure sublimed tri
phenylene starting from inexpensive commercially avail
able reactants. LCMS was used to study composition of
the mixture of products obtained upon oligomerization of
cyclohexanone in the presence of an alkali, possible rea
15 20 ret/min sons decreasing the yield of the target dodecahydrotri
phenylene in this step were identified. Taking into ac
b count commercial value of triphenylene, this method
seems promising, despite a moderate yield of the target
product.

Experimental
15 20 25 ret/min
1H and 13C NMR spectra were recorded on a Bruker Avance
c 400 spectrometer (400 and 100 MHz, respectively) in CDCl3,
using Me4Si as an internal standard. Melting points were mea
sured on a Boetius heating stage. Electron impact mass spectra
(EI) were measured on a SHIMADZU GCMSQP2010 Ultra
instrument.
The mass analyzer was a Bruker Daltonics (Bremen, Ger
20 25 30 ret/min many) MicrOTOFQ II mass spectrometer with an electrospray
Fig. 2. Chromatography pattern of cyclohexane trimers 3 (a), ionization source, a 6port divert valve and syringe pump
6 (b), and 7 (c). kd Scientific appliance with the flow rate 180 L h–1, and an
Agilent 1200 chromatograph with a diode array detector (DAD).
The instrument controls were performed with micrOTOFcon
in insignificant amount (one isomer with the low integral trol 2.3 patch 1 (Bruker Daltonics) software. The nominal reso
intensity of the peak). lution of the instrument was 17500. The instrument was operat
One of the major reasons of low efficiency of the pro ed in the positive ion mode with m/z range 50—900 Da. A 6 point
cess can be a low rate of cyclization reaction of the open external instrument mass scale was performed before each se
quence with lithium formate clustered by infusing 10 mmol L–1
chain trimer to the cyclic structure 3, as well as to its
of lithium hydroxide in a mixture of isopropanol—0.2% aqueous
dehydrated forms 6 and 7, which were also identified in
formic acid (1 : 1, v/v). The chromatograph was equipped by an
the reaction mixture. Agilent Eclipse XDB C18 column (150×4.6 mm) and worked in
We assume that in order to increase the yield of the the gradient mode (eluent acetonitrile—water, from 5 to 95% of
target dodecahydrotriphenylene 2, it is necessary to peri acetonitrile in the channel B from 0 to 30 min at the flow rate
odically add the starting cyclohexanone to the reaction 1.0 mL min–1).
mixture and to increase reaction time. Dodecahydrotriphenylene (2). Calcined anhydrous sodium
It should be also noted that, despite considerable hydroxide (6 g, 0.15 mol) was added to anhydrous freshly dis
amount of side products formed in the first step of the tilled cyclohexanone (60 mL, 0.58 mol) and the mixture ob
tained was stirred at room temperature for three days. Then,
process, the modified procedure used by us allows obtain
water (150 mL) was added to the reaction mixture with stirring,
ing dodecahydrotriphenylene 2 with sufficient purity with
a precipitate was filtered off, washed with 10% aqueous HCl and
out additional purification. water, and dried. The mixture of intermediate products without
We further made a number of changes in the procedure additional purification was added to polyphosphoric acid (40 g)
used for the preparation of dodecahydrotriphenylene 2 (the and stirred for 2 h at 150 C. Then, the reaction mixture was
dehydration step). In particular, we used polyphosphoric mixed with anhydrous sodium sulfate (100 g), placed into
acid instead of orthophosphoric acid because this reactant a Soxhlet extractor, and the product was continuously extracted
is more convenient in handling. Besides, we also changed with light petroleum (b.p. 40—70 C). A precipitate was filtered
the procedure used for the isolation of product 2: we ap off, washed with hexane, and dried. The yield was 24 g (52%),
m.p. 229—231 C. Found (%): C, 89.88; H, 10.01. C18H24. Cal
plied continuous extraction with light petroleum using
culated (%): C, 89.94; H, 10.06. 1H NMR, : 1.78 (m, 12 H,
a Soxhlet extractor. ArCH2CH2); 2.58 (m, 12 H, ArCH2CH2). 13C NMR, : 23.23,
Dehydrogenation of 2 leading to triphenylene 1 was 26.98, 132.77. MS (EI), m/z (%): 240 [M]+ (100).
also effected according to a modified procedure: 22 Triphenylene (1). A. Dodecahydrotriphenylene 2 (24 g, 0.1 mol)
the reaction was carried out under argon with the prep and 10% palladium/Sibunite (4 g) were heated for 10 h at 300 C
aration of sublimed triphenylene in 99% yield, which under argon over the surface cooled with running water. The
1542 Russ.Chem.Bull., Int.Ed., Vol. 63, No. 7, July, 2014 Kovalev et al.

sublimed product was mechanically removed from the surface. 9. T. Yatabe, M. A. Harbison, J. D. Brand, M. Wagner,
The yield was 22.57 g (99%), m.p. 196—198 C. Found (%): K. Müllen, P. Samori, J. P. Rabe, J. Mater. Chem., 2000,
C, 94.56; H, 5.21. C18H12. Calculated (%): C, 94.70; H, 5.30. 10, 1519.
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